KR101949181B1 - Block copolymer and polymer electrolyte membrane using the same - Google Patents

Abstract

The present invention relates to a block polymer and a polymer electrolyte membrane including the same, a membrane-electrode assembly including the polymer electrolyte membrane, a fuel cell including the membrane electrode assembly, and a redox flow cell including the polymer electrolyte membrane.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a block polymer and a polymer electrolyte membrane containing the block polymer.

This specification relates to a block polymer and a polymer electrolyte membrane comprising the block polymer. This specification claims the benefit of the filing date of Korean Patent Application No. 10-2016-0037903 filed on March 29, 2016, the entire contents of which are incorporated herein by reference.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction. The membrane electrode assembly (MEA) of a fuel cell is composed of a cathode, an anode, and an electrolyte membrane, that is, an ion conductive electrolyte membrane, as a portion where an electrochemical reaction of hydrogen and oxygen takes place.

A redox flow battery is a system in which an active substance contained in an electrolyte is oxidized-reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active material directly as electric energy to be. The unit cell of the redox flow battery includes an electrode, an electrolyte, and an ion exchange membrane (electrolyte membrane).

Fuel cells and redox flow cells are being researched and developed as a next generation energy source because of their high energy efficiency and eco - friendly characteristics with low emission of pollutants.

The most important components of the fuel cell and the redox flow cell are cation exchange polymer electrolyte membranes, which are: 1) excellent proton conductivity 2) cross-over of the electrolyte 3) strong chemical resistance 4) mechanical Physical properties and / or 4) low swelling ratio. The polymer electrolyte membrane is classified into a fluorine system, a partial fluorine system, and a hydrocarbon system. In the case of a partially fluorinated polymer electrolyte membrane, the polymer electrolyte membrane has an excellent physical and chemical stability and a high thermal stability due to its fluorine main chain. Also, like the fluorinated polymer electrolyte membrane, the partial fluorinated polymer electrolyte membrane has the advantages of the hydrocarbon-based polymer electrolyte membrane and the fluorinated polymer electrolyte membrane because the cation-transfer functional group is attached to the end of the fluorinated chain.

However, the partial fluorine-based polymer electrolyte membrane has a problem that the cation transfer function is relatively low because the fine phase separation of the cation-transfer functional groups and the control of aggregation phenomenon are not effectively performed. Therefore, studies have been made to secure a high cation conductivity by controlling the distribution of sulfonic acid groups and the separation of fine phases.

Korean Laid-Open Publication No. 2003-0076057

The present specification is intended to provide a block polymer and a polymer electrolyte membrane containing the block polymer.

The present invention relates to a hydrophobic block; And

Comprising a hydrophilic block,

Wherein the hydrophilic block comprises a unit derived from a compound represented by the following formula (1)

Wherein the hydrophobic block comprises a cationic group and a halogen group.

[Chemical Formula 1]

In formula (1)

A is ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M +, -PO 3 2- 2M +, _{-O (CF 2) m SO 3} H, -O (CF 2) m SO 3 - M +, -O (CF 2) m COOH, -O (CF 2) m COO - M +, -O (CF 2 ) _m PO ₃ H ₂ , -O (CF ₂ ) _m PO ₃ H ^- M ⁺ or -O (CF ₂ ) _m PO ₃ ^2- 2M ⁺

m is an integer of 2 to 6,

M is a Group 1 element,

R ₁ to R ₅ are the same or different from each other, and each independently hydrogen; A halogen group; Or a hydroxy group,

At least two of R ₁ to R ₅ are a halogen group; Or a hydroxy group,

R ₆ and R ₇ are the same or different and are each independently a halogen group,

L ₁ is a direct bond; -S-; -O-; -N (R) -; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

a is an integer of 0 to 2, and when a is 2, the structures in parentheses are the same or different from each other,

R is hydrogen; Or a substituted or unsubstituted alkyl group,

n is an integer of 2 to 10, and when n is 2 or more, the structures in parentheses are the same or different from each other.

The polymer electrolyte membrane comprising a block polymer according to one embodiment of the present disclosure easily forms a hydrophilic-hydrophobic phase-separation structure.

In addition, the polymer electrolyte membrane effectively controls the hydrophilic channel in the polyelectrolyte membrane by controlling the phase separation structure.

In addition, the polymer electrolyte membrane including the block polymer according to one embodiment of the present invention can simultaneously realize the advantages of the cationic polymer electrolyte membrane and the anionic polymer electrolyte membrane. That is, the polymer electrolyte membrane according to one embodiment of the present invention can simultaneously realize the characteristics of a cation and an anionic separator. In particular, when the conventional anion separator is used as a reference, the performance of the battery can be improved by improving the cation conductivity, which is a limit of the anion separator.

In addition, when the polymer electrolyte membrane according to one embodiment of the present invention is used in a fuel cell such as a redox flow battery, crossover of vanadium ions can be reduced and durability can be improved.

1 is a schematic view showing an electricity generation principle of a fuel cell.
2 is a schematic view showing an embodiment of a redox flow battery.
3 is a schematic view showing one embodiment of a fuel cell.
4 is an NMR spectrum of 1- (2-fluoro-5 - ((4-fluorophenyl) sulfonyl) phenyl) -N, N-dimethylmethanamine hydrochloride synthesized in Preparation Example 2.
5 is an NMR spectrum of a polymer synthesized by Reaction Scheme 1 of Example 1. Fig.
6 is an NMR spectrum of a polymer synthesized by Reaction Formula 3 of Example 2. Fig.

Hereinafter, the present invention will be described in more detail.

Whenever a component is referred to as " comprising ", it is to be understood that the component may include other components as well, without departing from the scope of the present invention.

As used herein, the term 'unit' means a structure in which a monomer is included in a polymer, and the monomer is bonded to the polymer by polymerization.

In this specification, the meaning of 'including unit' means that it is included in the main chain in the polymer.

는 인접한 치환기 또는 중합체의 주쇄와 결합함을 의미한다.In the present specification,

Quot; means bonding to the adjacent substituent or the backbone of the polymer.

In the present specification, the block polymer means a polymer composed of one block and one or more blocks different from the block connected to each other through the main chain of the polymer.

In one embodiment of the present disclosure, the block polymer may comprise a hydrophilic block and a hydrophobic block. Specifically, in one embodiment, the block polymer comprises a hydrophilic block comprising a unit represented by Formula 1; And a hydrophobic block comprising a cationic group and a halogen group.

As used herein, the term " hydrophilic block " means a block having an ion-exchange group as a functional group. Wherein the functional groups are ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M +, -PO 3 2- 2M +, _{-O (CF 2) m SO 3} H, -O (CF 2) m SO 3 - M +, -O (CF 2) m COOH, -O (CF 2) m COO - M +, -O (CF 2 ) _m PO ₃ H ₂ , -O (CF ₂ ) _m PO ₃ H ^- M ^+, and -O (CF ₂ ) _m PO ₃ ^{2 -} 2M ⁺ . Here, M may be a metallic element. That is, the functional group may be hydrophilic.

According to one embodiment of the present invention, the first unit represented by formula (1) may contain a functional group of A to thereby exhibit hydrophilicity.

The above-mentioned " block having an ion-exchange group " means a block represented by the number of ion-exchange groups per one structural unit constituting the block and an average of at least 0.5 or more blocks per one structural unit. It is more desirable to have an exchange.

In one embodiment of the present specification, the hydrophobic block includes a cationic group and a halogen group. In this case, improvement of the acid resistance and / or durability of the block polymer can be expected.

An embodiment of the present disclosure includes a hydrophobic block; And

Comprising a hydrophilic block,

Wherein the hydrophilic block comprises a unit derived from a compound represented by the following formula (1)

Wherein the hydrophobic block comprises a cationic group and a halogen group.

[Chemical Formula 1]

In formula (1)

A is ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M +, -PO 3 2- 2M +, _{-O (CF 2) m SO 3} H, -O (CF 2) m SO 3 - M +, -O (CF 2) m COOH, -O (CF 2) m COO - M +, -O (CF 2 ) _m PO ₃ H ₂ , -O (CF ₂ ) _m PO ₃ H ^- M ⁺ or -O (CF ₂ ) _m PO ₃ ^2- 2M ⁺

m is an integer of 2 to 6,

M is a Group 1 element,

R ₁ to R ₅ are the same or different from each other, and each independently hydrogen; A halogen group; Or a hydroxy group,

At least two of R ₁ to R ₅ are a halogen group; Or a hydroxy group,

R ₆ and R ₇ are the same or different and are each independently a halogen group,

L ₁ is a direct bond; -S-; -O-; -N (R) -; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

a is an integer of 0 to 2, and when a is 2, the structures in parentheses are the same or different from each other,

R is hydrogen; Or a substituted or unsubstituted alkyl group,

n is an integer of 2 to 10, and when n is 2 or more, the structures in parentheses are the same or different from each other.

In one embodiment of the present specification, the cationic group is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or may be represented by the following formula (2).

(2)

In formula (2)

L ₂ is a direct bond; -O-; -N (R ₁₄₎ -; -S-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

b is an integer of 1 to 10,

When b is 2 or more, two or more L < _{2 &gt}; s are the same or different from each other,

R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present invention, the hydrophobic block includes a unit derived from at least one of a compound represented by the following general formula (3) and a compound represented by the following general formula (4).

(3)

[Chemical Formula 4]

In formulas (3) and (4)

A ₁ and A ₂ are the same or different from each other, and each independently represents a hydroxyl group; Thiol group; Or a halogen group,

S ₁ and S ₂ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a structure represented by the following formula (2)

c and d are each an integer of 1 to 4,

c and d are each an integer of 2 or more, the structures in parentheses of 2 or more are the same or different from each other,

S ₃ and S ₄ are the same or different from each other, and each independently hydrogen; A halogen group; An alkyl group; Or a haloalkyl group,

E ₁ and E ₂ are the same or different from each other, and each independently represents a hydroxyl group; Thiol group; Or a halogen group, e is an integer of 1 to 4,

f is an integer of 1 to 3,

When e and f are each an integer of 2 or more, the structures in parentheses are equal to or different from each other,

S ₅ is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a structure represented by the following formula (2)

S ₃ and S ₄ are each independently a halogen group or a haloalkyl group, or S ₅ is a halogen group or a haloalkyl group,

The hydrophobic block is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; And one or two or more structures represented by the following formula (2)

(2)

In formula (2)

L ₂ is a direct bond; -O-; -N (R ₁₄₎ -; -S-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

b is an integer of 1 to 10,

When b is 2 or more, two or more L < _{2 &gt}; s are the same or different from each other,

R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment, Formula 4 may be represented by any of Formula 4-A to Formula 4-H.

[Chemical Formula 4-A]

[Chemical formula 4-B]

[Chemical formula 4-C]

[Chemical formula 4-D]

[Chemical Formula 4-E]

[Chemical Formula 4-F]

[Chemical formula 4-G]

[Chemical formula 4-H]

In formulas (4-A) to (4-H)

S ₅ and e are the same as in the formula (4)

S _{5 'and} S ₅ are as defined for, S ₅ and S _5' and the same or different from each other,

The definition of e 'is the same as e, and e and e' are the same or different.

In one embodiment of the present invention, the hydrophobic block includes at least one of units represented by the following general formula (3-1) and units represented by the following general formula (4-1).

[Formula 3-1]

[Formula 4-1]

In formulas (3-1) and (4-1)

The definition of S ₁ , S ₂ , c, d and f is the same as in the above formula (3) or (4).

In one embodiment, Formula (3-1) may be represented by Formula (3-1-1) below.

[Formula 3-1-1]

In Formula 3-1-1,

The definition of S ₁ , S ₂ , c and d is the same as in the above formula (3).

In one embodiment, the formula (4-1) may be represented by the following formula (4-1-1).

[Formula 4-1-1]

In Formula 4-1-1,

The definition of f is the same as in the above formula (4).

In another embodiment, Formula 4 is a compound of Formula 4-A-1, 4-B-1, 4-C-1, 4-D-1, 4-E- 4-G-1 and 4-H-1.

[Chemical formula 4-A-1]

[Formula 4-B-1]

[Chemical formula 4-C-1]

[Chemical formula 4-D-1]

[Chemical formula 4-E-1]

[Formula 4-F-1]

[Formula 4-G-1]

[Chemical formula 4-H-1]

In one embodiment of the present invention, the hydrophobic block may include a unit represented by the following formula (5).

[Chemical Formula 5]

In formula (5)

X ₁ is a direct bond; -CO-; -SO ₂ -; Or an alkylene group substituted with a halogen group,

X ₂ is -O-; Or -S-,

X ₃ is an alkylene group substituted by a direct bond or a halogen group,

k is 0 or 1,

p, q, r and s are each independently an integer of 0 to 4,

t, u, v and w are each independently 0 or 1,

The sum of t, u, v and w is at least 1,

The sum of p and t, the sum of q and u, the sum of r and v, and the sum of s and w are 4,

When p, q, r and s are each 2 or more, the substituents in the parentheses are the same or different from each other,

R ₂₁ to R ₂₄ are the same or different and are each independently hydrogen or a halogen group,

At least one of X ₁ and X ₃ is an alkylene group substituted with a halogen group, or at least one of R ₂₁ to R ₂₄ is a halogen group,

R ₃₁ to R ₃₄ are hydrogen; - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a cationic group represented by the following formula (2)

At least one of R ₃₁ to R ₃₄ is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a cationic group represented by the following formula (2)

(2)

In formula (2)

L ₂ is a direct bond; -O-; -N (R ₁₄₎ -; -S-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,

b is an integer of 1 to 10,

When b is 2 or more, two or more L < _{2 &gt}; s are the same or different from each other,

R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment, at least one of R ₃₁ and R ₃₂ is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a cationic group represented by the following formula (2).

In one embodiment of the present specification, a is 1.

In one embodiment of the present disclosure, L < ₁ > is -S-. The S atom is used as a linker of the - [C (R ₆ ) (R ₇ )] _n -A structure of the above formula (1) and the benzene ring. In this case, due to the electron withdrawing character of - [C (R ₆ ) (R ₇ )] _n -A connected to the S atom, it is possible to provide a polymer which is easy and stable in the formation of the polymer.

In one embodiment of the present invention, R ₆ and R ₇ are the same or different and are each independently a halogen group. Specifically, R ₆ and R ₇ are each independently F; Cl; Br; And < RTI ID = 0.0 > I. < / RTI >

In the case where the polymer containing the unit represented by the formula (1) is included in the polymer electrolyte membrane, if R ₆ and R _{7 in the} formula (1) are halogen groups, it is possible to facilitate the transfer of hydrogen ions by attracting electrons, There is an advantage that the structure of the polymer electrolyte membrane can be strengthened. More specifically, according to one embodiment of the present specification, the case where the R ₆ and R ₇ is fluorine, and the above advantage it can be maximized.

In one embodiment of the present specification, n is an integer of 2 to 10. In another embodiment of the present disclosure, n is an integer from 2 to 6.

Monomers comprising units of formula (1) according to one embodiment of the present disclosure can control the number of n. In this case, the length of the structure in the parentheses can be adjusted to facilitate the phase separation of the polymer electrolyte membrane, and the hydrogen ion migration of the polymer electrolyte membrane can be facilitated. Further, the monomer containing the unit of the formula (1) can control the difference in reactivity and the physical properties of the final polymer according to the control of the length of the structure in the parentheses as necessary.

In one embodiment of the present disclosure, n is 2.

In another embodiment, n is three.

In another embodiment, n is four.

In another embodiment, n is 5.

In another embodiment, n is six.

In another embodiment, n is 7.

In one embodiment of the present disclosure, n is eight.

In another embodiment, n is 9.

In one embodiment of the present disclosure, n is 10.

In one embodiment of the present specification, A is -SO ₃ H or -SO ₃ ^- M ⁺ .

In yet one embodiment, the A is an -SO ₃ H.

As described above, when A in formula (1) is -SO ₃ H or -SO ₃ ^- M ⁺ , a chemically stable polymer can be formed.

In one embodiment of the present disclosure, M is a Group 1 element.

In this specification, the Group 1 element may be Li, Na or K.

In one embodiment of the present specification, at least two of R ₁ to R ₅ are a halogen group; Or a hydroxy group.

In one embodiment of the present specification, at least two of R ₁ to R ₅ are a halogen group; Or a hydroxy group, and the remainder is hydrogen.

In one embodiment of the present invention, the case where R ₁ and R ₃ are a halogen group or a hydroxyl group, and R ₂ , R ₄ and R ₅ are hydrogen is superior in terms of polymerization.

In one embodiment of the present invention, the first unit derived from the compound represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-9).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

In one embodiment of the present invention, the hydrophilic block comprises a unit represented by Formula 1; And a unit derived from the compound represented by the formula (4).

In one embodiment of the present specification, S ₁ is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ .

In another embodiment, S ₂ is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ .

In one embodiment of the present specification, S ₅ is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ .

In one embodiment of the present invention, the hydrophilic block includes a unit represented by Formula 1, and may further include another unit. For example, the hydrophilic block may further include a unit derived from a compound represented by the following formula (3 ').

[Chemical Formula 3 ']

In formula (3 '),

A ' ₁ and A' ₂ are the same or different from each other, and each independently represents a hydroxyl group; Thiol group; Or a halogen group,

S ' ₁ and S' ₂ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

c 'and d' are each an integer of 1 to 4,

When c 'and d' are each an integer of 2 or more, the structures in parentheses of 2 or more are the same or different from each other,

S ' ₃ and S' ₄ are the same or different and are each independently hydrogen; A halogen group; An alkyl group; Or a haloalkyl group.

In one embodiment of the present invention, the hydrophobic block may contain a cationic group and a halogen group, and its position is not limited.

In one embodiment of the present disclosure, the block polymer comprises a unit represented by the following formula (A), (B), (C), or (D).

(A)

[Chemical Formula B]

≪ RTI ID = 0.0 &

[Chemical Formula D]

In Formulas A to D,

X ₁ , X ₂ , L ₁ , L ₂ , a, b and n are as defined above,

G is the same as the above-mentioned cationic group,

x and y are each independently a molar ratio of the block polymer and is a real number of more than 0 and less than 1,

x + y = 1.

,

또는

일 수 있다. In another embodiment, G in Formulas A through D is

,

or

Lt; / RTI >

In one embodiment of the present invention, R11 to R13 and R15 are alkyl groups.

In one embodiment of the present invention, R11 to R13 and R15 are methyl groups.

,

또는

일 수 있다.In another embodiment, G in Formulas A through D is

,

or

Lt; / RTI >

The polymer according to one embodiment of the present invention may have the following structure.

In one embodiment of the present disclosure, in the block polymer, the hydrophilic block and the hydrophobic block are contained in a molar ratio of 1: 0.001 to 1: 100. In one embodiment of the present invention, the hydrophilic block and the hydrophobic block are contained in the block polymer in a molar ratio of 1: 1 to 1: 0.001. In another embodiment, in the block polymer, the hydrophilic block and the hydrophobic block are contained in a molar ratio of 1: 0.1 to 1: 0.01.

In one embodiment of the present invention, it is preferable that the hydrophobic block is contained in an amount of 0.1 mol% to 50 mol%, more preferably 1 mol% to 10 mol%, based on the whole polymer of the block polymer.

In this case, the ion transfer ability of the block polymer can be increased.

In one embodiment of the present invention, the unit represented by the formula (1) in the hydrophilic block is contained in an amount of 0.01 to 100 mol% based on the hydrophilic block.

In one embodiment of the present disclosure, the number average molecular weight of the hydrophilic block is from 1,000 g / mol to 300,000 g / mol. In a specific embodiment, from 2,000 g / mol to 100,000 g / mol. And in another embodiment from 2,500 g / mol to 50,000 g / mol.

In one embodiment of the present disclosure, the number average molecular weight of the hydrophobic block is from 1,000 g / mol to 300,000 g / mol. In a specific embodiment, from 2,000 g / mol to 100,000 g / mol. And in another embodiment from 2,500 g / mol to 50,000 g / mol.

In one embodiment of the present disclosure, the block polymer may further comprise a brancher. In the present specification, the branculan serves to link or crosslink the polymer chain.

In the present specification, in the case of the block polymer further comprising the above-mentioned brancer, the brancer can constitute the main chain of the direct polymer and can improve the mechanical integration degree of the thin film. Specifically, the branched block polymer of the present invention can be obtained by polymerizing a branched hydrophilic block containing an acid substituent and a branched hydrophobic block containing no acid substituents, Without a post-sulfonation or cross-linking of the sulfonated polymer, a brancher can directly constitute the main chain of the polymer and maintain the mechanical integrity of the thin film The hydrophilic block that gives ion conductivity to the minority block and the thin film is alternately connected to the chemical bond.

In one embodiment of the present disclosure, the block polymer is selected from the group consisting of a branche derived from a compound represented by the following formula (6); Or a branche represented by the following general formula (7).

[Chemical Formula 6]

(7)

In formulas (6) and (7)

X is -S-; -O-; -CO-; -SO-; -SO ₂ -; -NR'-; A hydrocarbon-based or fluorine-

1 is an integer of 0 to 10,

When l is 2 or more, two or more X's are the same as or different from each other,

Y ₁ and Y ₂ are the same or different and are each independently selected from the group consisting of an aromatic ring substituted by one or more substituents selected from the group consisting of NR'R ", a hydroxyl group and a halogen group, or a group selected from the group consisting of a hydroxyl group and a halogen group An aliphatic ring substituted by one or two or more substituents,

R 'and R " are the same or different from each other and each independently represents hydrogen, an aromatic ring substituted with a halogen group, or an aliphatic ring substituted with a halogen group,

Z is a trivalent organic group.

Illustrative examples of such substituents are described below, but are not limited thereto.

In the present specification, the term "derived" means that the bond of the compound is broken or a new bond is formed as the substituent is released, and the unit derived from the compound may mean a unit connected to the main chain of the polymer. The unit may be included in the main chain in the polymer to constitute the polymer.

In one embodiment of the present invention, the unit derived from the compound represented by the formula (1) means that when at least two of R ₁ to R ₅ are a halogen group, the halogen group is connected to the main chain of the polymer while falling off . In another embodiment, when at least two of R ₁ to R ₅ are hydroxyl groups, the unit derived from the compound represented by the above-mentioned formula (1) means that the halogen group of a comonomer having a halogen group is dropped, And the like.

In one embodiment of the present invention, the unit derived from the compound represented by the general formula (4) is a compound wherein E ₁ and E ₂ are a hydroxyl group; Thiol group; Or a halogen group, which is dehydrogenated with a thiol group or a hydroxyl group, and is connected to the polymer main chain. The term " unit derived from " means that the resulting unit is connected to the main chain of the polymer while being hydrogenated, and may include a modification of a site connected to the main chain through post-treatment such as acid treatment or heat treatment.

For example, in one embodiment of the present disclosure, when E ₁ or E ₂ is a hydroxy group, a linking group of -O- may be provided in the polymer main chain, and when E ₁ and E ₂ are thiol groups, -S - may be provided. If necessary, the linking group of -S- in the polymer main chain can be converted into -SO ₂ - through an acid treatment.

Specifically, in the present specification, the branche derived from the compound of the formula (6) is an aromatic ring substituted with a halogen group of each of Y1 and Y2; Or a halogen group of an aliphatic ring substituted by a halogen group may act as a branching agent while being separated from an aromatic ring or an aliphatic ring. Specifically, two or more halogen groups may be released and act as a branching agent in the polymer.

The term " substituted " means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

In the present specification, the term "hydrocarbon-based" means an organic compound consisting solely of carbon and hydrogen, and includes, but is not limited to, straight chain, branched chain, and cyclic hydrocarbon. It may also include, but is not limited to, a single bond, a double bond or a triple bond.

In the present specification, the fluorine-based conjugate means that the carbon-hydrogen bond in the hydrocarbon system is partially or wholly substituted with fluorine.

In the present specification, the aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and may be monocyclic or polycyclic.

Specific examples of the aromatic hydrocarbon ring include monocyclic aromatic and naphthyl groups such as phenyl group, biphenyl group and terphenyl group, binaphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, tetracenyl group, , A fluorenyl group, an acenaphthacenyl group, a triphenylene group, a fluoranthene group, and the like, but are not limited thereto.

As used herein, the aromatic heterocycle means a structure containing at least one heteroatom such as O, S, N, Se, etc. instead of a carbon atom in the aromatic hydrocarbon ring. Specific examples include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, an isoquinoline group, an indole group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, A benzothiazole group, a benzothiophene group, a benzofuranyl group, a phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, A phenothiazinyl group, and a dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, the aliphatic ring may be an aliphatic hydrocarbon ring or an aliphatic heterocyclic ring, and may be monocyclic or polycyclic. Examples of the aliphatic ring include a cyclopentyl group, a cyclohexyl group, and the like, but are not limited thereto.

Examples of the organic group in the present specification include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an aralkyl group. The organic group may contain a bond or a substituent other than a hydrocarbon group such as a hetero atom in the organic group. The organic group may be linear, branched or cyclic.

In the present specification, a trivalent organic group means a trivalent organic group having three bonding sites.

The organic group may form a cyclic structure, may form a cyclic structure, and may form a bond including a heteroatom unless the effect of the invention is impaired.

Specifically, a bond containing a hetero atom such as an oxygen atom, a nitrogen atom, or a silicon atom. Specific examples thereof include an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond (-N═CR-: R represents a hydrogen atom or an organic group) A carbonate bond, a sulfonyl bond, a sulfinyl bond, an azo bond, and the like.

The cyclic structure may be an aromatic ring, an aliphatic ring, or the like, and may be monocyclic or polycyclic.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and in particular, there is a cyclopentyl group, a cyclohexyl group, and the like, but is not limited thereto.

In one embodiment of the present specification, l is 3 or more.

In one embodiment of the present disclosure, X is -S-.

In another embodiment, X is a haloalkylene group.

More specifically, X may be -CF ₃ CF ₃ -.

In another embodiment, X is -CH ₂ - a.

In another embodiment of the present disclosure, X is NR '.

In one embodiment of the present specification, Y1 and Y2 are the same as or different from each other, and each independently NR'R ".

In one embodiment of the present invention, Y1 and Y2 are the same or different from each other and each independently a halogen-substituted aromatic ring.

In one embodiment of the present specification, Y1 and Y2 are the same or different and are each independently a fluorine-substituted aromatic hydrocarbon ring.

In another embodiment, Y1 and Y2 are each a fluorine-substituted phenyl group. Specific examples thereof include 2,4-phenyl, 2,6-phenyl, 2,3-phenyl, 3,4-phenyl, and the like.

In one embodiment of the present invention, the compound represented by Formula 6 may be represented by any one of the following structures.

In the above structure, X and 1 are the same as defined in formula (6)

The definition of R " " is the same as that of R in formula (6).

According to one embodiment of the present invention, Z in the formula (7) may be represented by any one of the following formulas (7-1) to (7-4).

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

[Chemical Formula 7-4]

In the general formulas (7-1) to (7-4)

L ₁₁ to L ₁₇ are the same as or different from each other, and are each independently a direct bond; -S-; -O-; -CO-; Or -SO ₂ - and,

R ₁₀₀ to R ₁₁₀ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

r100, r101, r102, r105, r107, r108 and r109 are each an integer of 1 to 4,

r103, r104, r106 and r110 are each an integer of 1 to 3,

When each of r100 to r110 is an integer of 2 or more, the structures in parentheses of 2 or more are the same or different from each other.

In one embodiment of the present specification, L < ₁₁ > is -CO-.

In another embodiment, L ₁₁ is -SO ₂ -.

In another embodiment, L ₁₁ is -S-.

In another embodiment, L < ₁₂ > is -CO-.

In another embodiment, L ₁₂ is -SO ₂ -.

In another embodiment, L ₁₂ is -S-.

In one embodiment of the present disclosure, L ₁₃ is -CO-.

In another embodiment, L ₁₃ is -SO ₂ -.

In another embodiment, L ₁₃ is -S-.

In one embodiment of the present disclosure, L < ₁₄ > is -CO-.

In another embodiment, L ₁₄ is -SO ₂ -.

In one embodiment of the present specification, L < ₁₅ > is a direct bond.

In another embodiment, L < ₁₆ > is a direct bond.

In another embodiment, L ₁₇ is a direct bond.

In one embodiment of the present specification, R ₁₀₀ to R ₁₁₀ are hydrogen.

In one embodiment of the present specification, R ₁₀₆ is a halogen group.

In another embodiment, R < ₁₀₆ > is fluorine.

Further, in one embodiment of the present invention, the branching agent represented by the general formula (7) may be represented by any one of the following structures.

,

,

,

,

,

,

,

,

,

,

,

,

.

,

,

.

In one embodiment of the present disclosure, the weight average molecular weight of the polymer is from 500 g / mol to 5,000,000 g / mol. In another embodiment of the present disclosure, the weight average molecular weight of the polymer is from 10,000 g / mol to 3,000,000 g / mol. When the weight average molecular weight of the polymer is in the above range, the mechanical properties of the electrolyte membrane containing the polymer are not lowered, the solubility of the appropriate polymer is maintained, and the electrolyte membrane can be easily produced.

The present specification also provides a polymer electrolyte membrane comprising the above-described block polymer.

When a block polymer containing a unit represented by the formula (1) according to an embodiment of the present invention is included, it has a high mechanical strength and a high ion conductivity and can facilitate the phase separation of the electrolyte membrane.

As used herein, the term " electrolyte membrane " is a membrane capable of ion exchange, and includes a membrane, an ion exchange membrane, an ion transport membrane, an ion conductive membrane, a membrane, an ion exchange membrane, A transfer electrolyte membrane, an ion conductive electrolyte membrane, and the like.

The polymer electrolyte membrane according to one embodiment of the present invention comprises a hydrophilic block containing the unit represented by Formula 1; And a block polymer comprising a hydrophobic block comprising at least one cationic side chain, with the proviso that the hydrophobic block comprises at least one cationic side chain.

According to one embodiment of the present invention, the ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.5 S / cm or less. In another embodiment, the ionic conductivity of the polymer electrolyte membrane is 0.01 S / cm or more and 0.3 S / cm or less.

In one embodiment of the present invention, the ionic conductivity of the polymer electrolyte membrane can be measured under a humidifying condition. In the present specification, the humidifying condition may mean a relative humidity (RH) of 10% to 100%.

In one embodiment of the present invention, the ion exchange capacity (IEC) value of the polymer electrolyte membrane is 0.01 mmol / g to 5 mmol / g. When the ion exchange capacity value is in the range, the ion channel in the polymer electrolyte membrane is formed, and the polymer can exhibit ion conductivity.

In one embodiment of the present invention, the thickness of the polymer electrolyte membrane is 1 탆 to 500 탆. The polymer electrolyte membrane having the above-described range of thickness can reduce electric short and cross-over of the electrolyte material and exhibit excellent cation conductivity.

The disclosure also includes an anode; Cathode; And the above-described polymer electrolyte membrane provided between the anode and the cathode.

The membrane-electrode assembly (MEA) means a junction body of an electrode (cathode and anode) where an electrochemical catalytic reaction of fuel and air takes place and a polymer membrane in which hydrogen ions are transferred, and the electrode (cathode and anode) It is a single integral unit.

The membrane-electrode assembly of the present invention can be produced by a conventional method known in the art, such that the catalyst layer of the anode and the catalyst layer of the cathode are in contact with the electrolyte membrane. For example, the cathode; Anode; And an electrolyte membrane positioned between the cathode and the anode in close contact with each other at 100 ° C to 400 ° C.

The anode electrode may include an anode catalyst layer and an anode gas diffusion layer. The anode gas diffusion layer may again include an anode microporous layer and an anode electrode substrate.

The cathode electrode may include a cathode catalyst layer and a cathode gas diffusion layer. The cathode gas diffusion layer may again include a cathode microporous layer and a cathode electrode substrate.

FIG. 1 schematically shows an electricity generating principle of a fuel cell. In a fuel cell, a basic unit for generating electricity is a membrane electrode assembly (MEA), which includes an electrolyte membrane 100 and an electrolyte membrane 100, And an anode 200a and a cathode 200b electrodes formed on both sides of the cathode 200a. 1 showing the principle of electricity generation of a fuel cell, in the anode 200a, oxidation reaction of hydrogen such as hydrogen or hydrocarbons such as methanol and butane occurs, hydrogen ions (H +) and electrons (e-) are generated, The hydrogen ions move through the electrolyte membrane 100 to the cathode 200b. In the cathode 200b, hydrogen ions transferred through the electrolyte membrane 100 react with an oxidizing agent such as oxygen and electrons to generate water. This reaction causes electrons to migrate to the external circuit.

The catalyst layer of the anode electrode is preferably a catalyst selected from the group consisting of platinum, ruthenium, osmium, platinum-ruthenium alloy, platinum-osmium alloy, platinum-palladium alloy and platinum- Lt; / RTI > The catalyst layer of the cathode electrode is a place where a reduction reaction of an oxidizing agent occurs, and a platinum or platinum-transition metal alloy can be preferably used as a catalyst. The catalysts can be used not only by themselves but also by being supported on a carbon-based carrier.

The process of introducing the catalyst layer can be performed by a conventional method known in the art. For example, the catalyst ink may be directly coated on the electrolyte membrane or coated on the gas diffusion layer to form the catalyst layer. The method of coating the catalyst ink is not particularly limited, but spray coating, tape casting, screen printing, blade coating, die coating or spin coating may be used. The catalyst ink may typically consist of a catalyst, a polymer ionomer and a solvent.

The gas diffusion layer serves as a current conductor and serves as a passage for reacting gas and water, and has a porous structure. Therefore, the gas diffusion layer may include a conductive base material. As the conductive substrate, carbon paper, carbon cloth or carbon felt can be preferably used. The gas diffusion layer may further include a microporous layer between the catalyst layer and the conductive base. The microporous layer can be used to improve the performance of the fuel cell under low humidification conditions and serves to reduce the amount of water flowing out of the gas diffusion layer to make the electrolyte membrane sufficiently wet.

One embodiment of the present disclosure includes at least two membrane-electrode assemblies; A stack including a bipolar plate disposed between the membrane-electrode assemblies; A fuel supply unit for supplying fuel to the stack; And an oxidant supply unit for supplying an oxidant to the stack.

Fuel cells are energy conversion devices that convert the chemical energy of a fuel directly into electrical energy. That is, a fuel cell uses a fuel gas and an oxidizing agent, and generates electricity using electrons generated during the oxidation-reduction reaction.

The fuel cell can be manufactured according to a conventional method known in the art using the above-described membrane-electrode assembly (MEA). For example, the membrane electrode assembly (MEA) and the bipolar plate may be fabricated.

The fuel cell of the present invention comprises a stack, a fuel supply, and an oxidant supply.

3 schematically shows the structure of a fuel cell, which includes a stack 60, an oxidant supply unit 70, and a fuel supply unit 80. [

The stack 60 includes one or more of the membrane electrode assemblies described above and includes a separator interposed therebetween when two or more membrane electrode assemblies are included. The separator serves to prevent the membrane electrode assemblies from being electrically connected and to transfer the fuel and oxidant supplied from the outside to the membrane electrode assembly.

The oxidant supply part 70 serves to supply the oxidant to the stack 60. As the oxidizing agent, oxygen is typically used, and oxygen or air can be injected into the pump 70 and used.

The fuel supply unit 80 serves to supply the fuel to the stack 60 and includes a fuel tank 81 for storing the fuel and a pump 82 for supplying the fuel stored in the fuel tank 81 to the stack 60 Lt; / RTI > As the fuel, gas or liquid hydrogen or hydrocarbon fuel may be used. Examples of hydrocarbon fuels include methanol, ethanol, propanol, butanol or natural gas.

The fuel cell may be a polymer electrolyte fuel cell, a direct liquid fuel cell, a direct methanol fuel cell, a direct formic acid fuel cell, a direct ethanol fuel cell, or a direct dimethyl ether fuel cell.

When the electrolyte membrane according to one embodiment of the present invention is used as an ion exchange membrane of a fuel cell, the above-described effect can be obtained.

In addition, one embodiment of the present disclosure includes a positive electrode cell including a positive electrode and a positive electrode electrolyte; A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And a polymer electrolyte membrane according to an embodiment of the present invention provided between the anode cell and the cathode cell.

Redox Flow Battery (Redox Flow Battery) is a system in which an active substance contained in an electrolyte is oxidized-reduced to be charged and discharged. An electrochemical storage device that stores chemical energy of an active material directly as electric energy to be. The redox flow battery utilizes the principle of charging and discharging electrons by receiving electrons when an electrolyte containing an active material having a different oxidation state meets the ion exchange membrane. Generally, a redox flow battery is composed of a tank containing an electrolyte solution, a battery cell in which charging and discharging occur, and a circulation pump circulating the electrolyte between the tank and the battery cell, and the unit cell of the battery cell includes an electrode, Exchange membrane.

When the electrolyte membrane according to one embodiment of the present invention is used as the ion exchange membrane of the redox flow cell, the above-described effect can be obtained.

The redox flow cell of the present specification can be produced according to a conventional method known in the art, except that it includes a polymer electrolyte membrane according to one embodiment of the present specification.

2, the redox flow battery is divided into a positive electrode cell 32 and a negative electrode cell 33 by an electrolyte film 31. As shown in FIG. The anode cell 32 and the cathode cell 33 each include an anode and a cathode. The anode cell (32) is connected to the anode tank (10) for supplying and discharging the anode electrolyte (41) through a pipe. The cathode cell 33 is also connected to a cathode tank 20 for supplying and discharging the cathode electrolyte 42 through a pipe. The electrolytic solution is circulated through the pumps 11 and 21, and an oxidation / reduction reaction (that is, a redox reaction) in which the oxidation number of ions is changed occurs, thereby charging and discharging occur in the anode and the cathode.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

< Manufacturing example  1>

Synthesis of 2- (bromomethyl) -1-fluoro-4 - ((4-fluorophenyl) sulfonyl) benzene

(0.75 mol) of 1-fluoro-4 - ((4-fluorophenyl) sulfonyl) -2-methylbenzene was dissolved in chloroform , And 18.1 g (74.5 mmol) of benzoyl peroxide was added. 398 g (2.24 mol) of N-bromosuccinimide was slowly added dropwise, and the temperature of the reaction mixture was raised to 65 ° C and the mixture was stirred at the same temperature for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed several times with saturated aqueous NaHCO ₃ solution. The organic layer thus obtained was dried over magnesium sulfate (MgSO ₄ ) and distilled to obtain 2- (bromomethyl) -1-fluoro-4 - ((4-fluorophenyl) sulfonyl) benzene in a crude state The crude compound thus obtained was used in the next reaction without further purification and purification. The crude product was purified by silica gel column chromatography to obtain 2- (bromomethyl) -1-fluoro-4- (4-fluorophenyl) sulfonyl) benzene.

< Manufacturing example  2>

Synthesis of 1- (2-fluoro-5 - ((4-fluorophenyl) sulfonyl) phenyl) -N, N-dimethylmethanamine hydrochloride

After the crude 2- (bromomethyl) -1-fluoro-4 - ((4-fluorophenyl) sulfonyl) benzene obtained in Preparation Example 1 was dissolved in 1500 ml of tetrahydrofuran (THF) After cooling to 0 캜, 420 g (3.73 mol) of dimethylamine (Dimehtylamine 40 wt% in H ₂ O) was slowly added dropwise. The temperature of the reaction mixture was raised to room temperature and then stirred at room temperature for 4 hours. The solvent was removed by distillation under reduced pressure, diluted with ethyl acetate, and 1N HCl was added dropwise. The water layer thus obtained was washed several times with ethyl acetate to remove impurities, and the acidic water layer was distilled under reduced pressure to obtain a solid compound in a salt form of HCl. The solid compound thus obtained was added with methylene chloride and stirred at room temperature in a slurry state, followed by filtration and drying under N ₂ gas to obtain the final compound 1- (2-fluoro-5 - ((4-fluorophenyl) Sulfonyl) phenyl) -N, N-dimethylmethanamine hydrochloride was obtained in 42% yield (2 step yield).

The NMR spectrum of the above 1- (2-fluoro-5 - ((4-fluorophenyl) sulfonyl) phenyl) -N, N-dimethylmethanamine hydrochloride is shown in FIG.

< Example  1>

[Reaction Scheme 1]

Each monomer and potassium carbonate (K ₂ CO ₃ : molar ratio 4) of the above reaction scheme 1 were mixed at a ratio of 30 wt% of methylpyrrolidone (NMP) and 20 wt% of benzene, and the mixture was heated at 140 ° C. for 4 hours, 180 ° C. For 16 hours to prepare the polymer of the above reaction formula (1). The 1 H-NMR of the polymer of the above Reaction Formula 1 is as shown in FIG. 5, and a polymer was dissolved in dimethylacetamide (DMAC), and then a 1 H-NMR experiment was conducted in a CDCl ₃ solvent.

[Reaction Scheme 2]

Each of the monomers and potassium carbonate (K2CO3: molar ratio 4) of the reaction formula 2 was mixed with 30 wt% of methylpyrrolidone (NMP) and 20 wt% of benzene to the polymer synthesized in the reaction scheme 1, , And polymerized at 180 ° C for 16 hours to prepare a polymer of the above reaction formula (2).

< Example  2>

The polymer of the reaction formula 2 obtained in Example 1 was dissolved in dimethylacetamide (DMAC) at a concentration of 5 wt%, and then 5 eq of methyliodide was added thereto. The mixture was allowed to react at room temperature for 6 hours to finally obtain the polymer of the following reaction formula 3 . The NMR spectrum of the final polymer of Reaction Scheme 3 is shown in Fig.

[Reaction Scheme 3]

< Comparative Example >

Example 2 The vanadium permeability of the electrolyte membrane using the copolymer and Nafion 115 was measured and is shown in Table 1 below.

VO ²⁺ permeability
(cm ² / min) x 10 ^-6 Example 2 0.48 Nafion 115 (comparative example) 5.84

The vanadium ion permeability was measured by charging a 1M VOSO ₄ in 2M H ₂ SO ₄ solution on one side and a 1M MgSO ₄ in 2M H ₂ SO ₄ solution on the other side and then installing an electrolyte membrane between the two solutions, The concentration of VO ²⁺ in the MgSO ₄ in 2M H ₂ SO ₄ solution was measured.

The active area was measured at 7.69 cm ² and the volume was measured at 200 ml at room temperature.

In the case of the electrolyte membrane containing the copolymer according to Example 2, the permeability of the vanadium ion was lower than that of the conventional Nafion electrolyte membrane due to the presence of the cationic functional group in the main chain of the electrolyte membrane as compared with the Nafion 115 electrolyte membrane It can be seen that it fell greatly. As a result, the crossover of the vanadium ion (VO ²⁺ ) by the Donnan effect can be effectively suppressed, so that the electrolyte membrane including the copolymer according to one embodiment of the present invention has excellent performance Can be predicted.

Further, since the main chain of the electrolyte membrane contains the fluorine element, it can be predicted that it can greatly contribute to the improvement of the durability of the electrolyte membrane.

Therefore, when the fuel cell or redox flow battery is manufactured using the electrolyte membrane according to the present invention, the efficiency of the battery can be increased.

100: electrolyte membrane
200a: anode
200b: cathode
10, 20: tank
11, 21: pump
31: electrolyte membrane
32: anode cell
33: cathode cell
41: anode electrolyte
42: cathode electrolyte
60: Stack
70: oxidant supplier
80: fuel supply unit
81: Fuel tank
82: Pump

Claims (16)

Hydrophobic blocks; And
Comprising a hydrophilic block,
Wherein the hydrophilic block comprises a unit derived from a compound represented by the following formula (1)
Wherein the hydrophobic block comprises a cationic group and a halogen group:
[Chemical Formula 1]

In formula (1)
A is ^{_{-SO 3 H, -SO 3 - M}} +, -COOH, -COO - M +, -PO 3 H 2, -PO 3 H - M +, -PO 3 2- 2M +, _{-O (CF 2) m SO 3} H, -O (CF 2) m SO 3 - M +, -O (CF 2) m COOH, -O (CF 2) m COO - M +, -O (CF 2 ) _m PO ₃ H ₂ , -O (CF ₂ ) _m PO ₃ H ^- M ⁺ or -O (CF ₂ ) _m PO ₃ ^2- 2M ⁺
m is an integer of 2 to 6,
M is a Group 1 element,
R ₁ to R ₅ are the same or different from each other, and each independently hydrogen; A halogen group; Or a hydroxy group,
At least two of R ₁ to R ₅ are a halogen group; Or a hydroxy group,
R ₆ and R ₇ are the same or different and are each independently a halogen group,
L ₁ is a direct bond; -S-; -O-; -N (R) -; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
a is an integer of 0 to 2, and when a is 2, the structures in parentheses are the same or different from each other,
R is hydrogen; Or a substituted or unsubstituted alkyl group,
n is an integer of 2 to 10, and when n is 2 or more, the structures in parentheses are the same or different from each other. The method according to claim 1,
The cationic group is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a block polymer which is a cationic group represented by the following formula (2):
(2)

In formula (2)
L ₂ is a direct bond; -O-; -N (R ₁₄₎ -; -S-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
b is an integer of 1 to 10,
When b is 2 or more, two or more L &lt; _{2 &gt}; s are the same or different from each other,
R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. The method according to claim 1,
Wherein the hydrophobic block comprises a unit derived from at least one of a compound represented by the following general formula (3) and a compound represented by the following general formula (4)
(3)

[Chemical Formula 4]

In formulas (3) and (4)
A ₁ and A ₂ are the same or different from each other, and each independently represents a hydroxyl group; Thiol group; Or a halogen group,
S ₁ and S ₂ are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a structure represented by the following formula (2)
c and d are each an integer of 1 to 4,
c and d are each an integer of 2 or more, the structures in parentheses of 2 or more are the same or different from each other,
S ₃ and S ₄ are the same or different from each other, and each independently hydrogen; A halogen group; An alkyl group; Or a haloalkyl group,
E ₁ and E ₂ are the same or different from each other, and each independently represents a hydroxyl group; Thiol group; Or a halogen group,
e is an integer of 1 to 4,
f is an integer of 1 to 3,
When e and f are each an integer of 2 or more, the structures in parentheses are equal to or different from each other,
S ₅ is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; A substituted or unsubstituted heterocyclic group; - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a structure represented by the following formula (2)
S ₃ and S ₄ are each independently a halogen group or a haloalkyl group, or S ₅ is a halogen group or a haloalkyl group,
The hydrophobic block is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; And one or two or more structures represented by the following formula (2)
(2)

In formula (2)
L ₂ is a direct bond; -O-; -N (R ₁₄₎ -; -S-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
b is an integer of 1 to 10,
When b is 2 or more, two or more L &lt; _{2 &gt}; s are the same or different from each other,
R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. The method of claim 3,
The formula 3 is represented by the following formula 3-1,
Wherein the formula 4 is a block polymer represented by the following formula 4-1:
[Formula 3-1]

[Formula 4-1]

In formulas (3-1) and (4-1)
The definition of S ₁ , S ₂ , c, d and f is the same as in the above formula (3) or (4). The method according to claim 1,
Wherein the hydrophobic block comprises a unit represented by the following formula (5):
[Chemical Formula 5]

In formula (5)
X ₁ is a direct bond; -CO-; -SO ₂ -; Or an alkylene group substituted with a halogen group,
X ₂ is -O-; Or -S-,
X ₃ is an alkylene group substituted by a direct bond or a halogen group,
k is 0 or 1,
p, q, r and s are each independently an integer of 0 to 4,
t, u, v and w are each independently 0 or 1,
The sum of t, u, v and w is at least 1,
The sum of p and t, the sum of q and u, the sum of r and v, and the sum of s and w are 4,
When p, q, r and s are each 2 or more, the substituents in the parentheses are the same or different from each other,
R ₂₁ to R ₂₄ are the same or different and are each independently hydrogen or a halogen group,
At least one of X ₁ and X ₃ is an alkylene group substituted with a halogen group, or at least one of R ₂₁ to R ₂₄ is a halogen group,
R ₃₁ to R ₃₄ are hydrogen; - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a cationic group represented by the following formula (2)
At least one of R ₃₁ to R ₃₄ is - (L ₂ ) _b -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (L ₂ ) _{b -} P ⁺ R ₁₁ R ₁₂ R ₁₃ ; Or a cationic group represented by the following formula (2)
(2)

In formula (2)
L ₂ is a direct bond; -O-; -N (R ₁₄₎ -; -S-; -SO ₂ -; Or a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms,
b is an integer of 1 to 10,
When b is 2 or more, two or more L &lt; _{2 &gt}; s are the same or different from each other,
R ₁₁ to R ₁₅ are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms. The method according to claim 1,
Wherein the unit derived from the compound represented by the formula (1) is represented by any one of the following formulas (1-1) to (1-9):
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Chemical Formula 1-6]

[Chemical Formula 1-7]

[Chemical Formula 1-8]

[Chemical Formula 1-9]

. The method according to claim 1,
Wherein the hydrophilic block and the hydrophobic block are contained in the block polymer in a molar ratio of 1: 0.001 to 1: 100. The method according to claim 1,
Wherein the block polymer further comprises a branche. The method according to claim 1,
Wherein the block polymer has a weight average molecular weight of from 500 g / mol to 5,000,000 g / mol. A polymer electrolyte membrane comprising the block polymer according to any one of claims 1 to 9. The method of claim 10,
Wherein the polymer electrolyte membrane has an ion conductivity of 0.01 S / cm to 0.5 S / cm. The method of claim 10,
Wherein the polymer electrolyte membrane has an ion exchange capacity (IEC) value of 0.01 mmol / g to 5 mmol / g. The method of claim 10,
Wherein the polymer electrolyte membrane has a thickness of 1 占 퐉 to 500 占 퐉. Anode; Cathode; And a polymer electrolyte membrane according to claim 10 provided between the anode and the cathode. At least two membrane-electrode assemblies according to claim 14;
A stack including a bipolar plate disposed between the membrane-electrode assemblies;
A fuel supply unit for supplying fuel to the stack; And
And an oxidant supplier for supplying the oxidant to the stack. A positive electrode including a positive electrode and a positive electrode electrolyte;
A negative electrode cell comprising a negative electrode and a negative electrode electrolyte; And
The redox flow battery according to claim 10, which is provided between the positive electrode cell and the negative electrode cell.

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